Anthraquinonyl-triazines

ABSTRACT

ANTHRAQUINONE DYESTUFFS OF THE FORMULA   ((4-X,6-HAL-S-TRIAZIN-2-YL)-N(-LOWER ALKYL)-CO-N(-R))N-D   WHEREIN D IS AN ANTHRAQUINONE DYESTUFF RADICAL;   -N(-R)-   IS CONNECTED TO AN AROMATIC RING CARBON OF D; R IS H OR LOWER ALKYL; HAL IS F, CL OR BR; N IS ONE OF THE INTEGERS 1 OR 2 AND X IS A MONOVALENT ELECTRON-DONOR SUBSTITUENT, SELECTED FROM THE GROUP OF LOWER ALKOXY, PHENOXY, HALOGEN-SUBSTUTED PHENOXY, LOWER ALKYL-SUBSTITUTED PHENOXY, LOWER, ALKOXY-SUBSTITUTED PHENOXY, LOWER ALKYLTHIO, PHENYLTHIO, HALOGEN-SUBSTITUED PHENYLTHIO,LOWER ALKYYL-SUBSTITUTED PHENYLTHIO, LOWER ALKOXY-SUBSTITUTED PHENYLTHIO, LOWER ALKYLAMINO, DI(LOWER) ALKYLAMINO, PHENYLAMINO, NLOWER ALKYL-N-PHENYLAMINO, N-LOWER ALKYL-N-HALOGENPHENYLAMINO, N-LOWER ALKYL-N-LOWER ALKYLPHENYLAMINO, N-LOWER, ALKYL-N-LOWER, ALKOXYPHENYLAMINO, PIPERDINO OR MORPHOLINO, HALOGEN BEING CHLORO OR BROMO.

United States Patent Office 3,660,393 Patented May 2, 1972 US. Cl. 260-249 3 Claims ABSTRACT OF THE DISCLOSURE Anthraquinone dyestuffs of the formula l l na1o -I IALN D N N (lower alkyl) i X n wherein D is an anthraquinone dyestuff radical;

R l N is connected to an aromatic ring carbon of D; R is H or lower alkyl; Hal is F, C1 or Br; n is one of the integers 1 or 2 and X is a monovalent electron-donor substituent,

selected from the group of lower alkoxy, phenoxy, halogen-substituted phenoxy, lower alkyl-substituted phenoxy, lower alkoxy-substituted phenoxy, lower alkylthio, phenylthio, halogen-substituted phenylthio, lower alkyl-substituted phenylthio, lower alkoxy-substituted phenylthio, lower alkylamino, di(lower)alkylamino, phenylamino, N- lower alkyl-N-phenylamino, N-lower alkyl-N-halogenphenylamino, N-lower alkyl-N-lower alkylphenylamino, N-lower alkyl-N-lower alkoxyphenylamino, piperidino or morpholino, halogen being chloro or bromo'.

This application is a divisional application of application Ser. No. 800,300 filed November 8, 1968, which application in turn is a continuation application of application Ser. No. 517,998, filed J an. 3, 1966, now abandoned which latter application is in turn a continuation-in-part of application Ser. No. 380,677 filed July 6, 1964 now abandoned.

The present invention relates to reactive dyestuffs, processes for the production thereof, their use for the dyeing of organic textile fibers containing hydroxyl and/ or amino groups, as well as, as industrial product, the fiber materials dyed with the aid of these dyestuffs.

It has been found that dyestuffs which, surprisingly, can be fixed onto textile fibers containing hydroxyl and amino groups and allord dyeings of good fastness properties, are obtained by reacting one mol of an organic dyestuff of the formula D represents the radical of an organic dyestuff capable of withstanding the conventional conditions of dyeing textile fibers containing in their molecule hydroxyl wherein and/or amino groups with fiber-reactive dyestuffs, and subsequent fixation by thermofixing or steaming,

R represents hydrogen or lower alkyl, and

n represents 1 or 2,

with n mol of a compound capable of yielding the radical of the formula wherein Hal represents halogen of one of the atomic numbers 9,

17 or 35, i.e. fluorine, chlorine or bromine, and

X represents a monovalent electron-donating substituent containing a hetero atom of one of the atomic numbers 7, 8 and 16, by way of which atom said substituent is linked to the triazinyl ring in Formula II, and the molecular weight of which substituent does not exceed 200,

to form a dyestuff of the formula N (|J ClTIGOI I D N bl (lower alkyl) I X n Hal (III) wherein D, R and n have the same meanings as in Formula I, and Hal and X have the same meanings as in Formula II,

or by forming the reactive dyestuffs of Formula III from components of which at least one contains the radical of Formula II bound by way of an amino group of the formula Lower as used in this specification and in the appended claims in connection with alkyl, alkoxy and the like radicals means that these radicals have from 1 to 5 carbon atoms, unless expressly stated otherwise.

It would have been expected that a triazinyl radical which is attached to a urea bridge, as it is the case in Formula III, would not resist the severe conditions of dyeing textile fibers with fiber-reactive dyestuffs, namely, in particular, strong alkaline dye liquors of pH values in the order of 10 and higher, and treatment, at least during subsequent thermofixation or steaming at elevated temperatures of about to C. in a strongly alkaline medium, but that the triazinyl lower alkylamino radical would be split from the CO-NR-- bridge of Formula 111 during dyeing, so that no fixation of the dyestuffs to the fiber molecule could take place.

Indeed, this would occur if X in Formula III would represent an electron-accepting substituent. Furthermore, intermediates with such a substituent would not be readily available.

It is one surprising feature of the dyestuffs according to the invention that the bond of the triazinyl radical to the urea bridge in the dyestuffs of Formula III, in which X has the above-defined meaning, and via the urea bridge to the dyestufE-character imparting principal moiety of the molecule in Formula III is so strong that the severe conditions of reactive dyeing, especially on cotton but also on wool or nylon, are withstood without substantial decomposition, and that commercially useful dyeings of satisfactory fastness properties are obtained.

The reaction between the fiber molecule and the reactive dyes falling under Formula III takes place substantially entirely by splitting off the Hal substituent from the triazinyl reactive group.

In Formulas I and III, D represents in particular the radical of, for example, a mono-, disor poly-azo dyestuff which may contain heavy metal in complex bond, an anthraquinone, a nitro or a phthalocyanine dyestuff.

In those compounds of Formula III in which D represents the radical of an azo dyestulf it is, for example, the radical of a monoazo dyestuff of the benzene-azobenzene, benzene-azo-naphthalene, benzene-azo-pyrazole, benzene-azo-acetoacetylarylamide, naphthalene-azo-naphthalene and naphthalene-azo-pyrazole series, or the radical of a disazo dyestuff of the benzene-azo-benzene-azo-benzene, benzene-azo-naphthalene-azo-benzene and naphthalene-azo-benzene-azo-benzene series, all of which may be free from or may contain heavy metal in complex bond, or of a metal-containing formazane dyestuff.

In those compounds of Formula III in which D is the radical of an anthraquinone dyestuff, it is preferably a 1- amino-4-phenylaminoor 1-amino-4-diphenylamino-anthraquinone radical.

When D is the radical of a phthalocyanine dyestuff, it is preferably the radical of phthalocyanine sulfonic acid alkylamide or arylamide, which preferably contains sulfonic acid groups.

The organic dyestuffs of Formula I contain the groups either in the internal, principal dyestuff structure or at an external substituent, such as at the benzene ring of benzoylamino or of phenylamino groups.

The dyestuffs mentioned can contain shadeand fastness properties-influencing substituents.

Such shadeand fastness properties-influencing types of substitution in the dyestuffs according to the invention are: fluorine, chlorine, bromine, lower alkyl groups having straight or branched chains such as the methyl, ethyl, propyl, isopropyl, n-butyl, tert. butyl and amyl group, cycloalkyl groups such as the cyclohexyl and the methyl cyclohexyl group, aralkyl groups such as the benzyl or phenethyl group, ether groups such as lower alkoxy, e.g. methoxy, ethoxy, or benzyloxy or phenoxy group, lower alkyl-sulfonyl, carboxylic acid and sulfonic acid groups, acylamino groups such as the acetylamino, chloroacetylamino, fl-bromopropionylamino, phenylamino and benzoylamino group, carboxylic acid amide and sulfonic acid amide groups which may be N-substituted, also the nitro, amino, carbamido, amino-phenyl SO NHSO and hydroxyl groups.

R, when representing a lower alkyl group is, for example, the methyl or ethyl group; preferably, however, it represents hydrogen.

The reactivity of dyestuffs of Formula III according to the invention in which Hal is fluorine is superior to that of dyestuffs in which Hal is chlorine. They can thus be fixed onto the fiber at relatively low temperatures, whereas dyestuffs in which Hal is chlorine require higher fixing temperatures or stronger bases, e.g. sodium hydroxide, as acid-binding agents.

The lower alkyl substituent at the nitrogen atom in Formula III to which the triazinyl radical is attached is, for example, methyl, ethyl, isopropyl or butyl.

The monovalent electron-donating substituent X which is of a molecular weight not exceeding 200, and preferably below 150, represents, for example, ether groups such as an alkoxy group, e.g. the methoxy or the ethoxy group; an aryloxy group, in particular the unsubstituted phenoxy group, but also a phenoxy group substituted by halogen, e.g. chlorine, by lower alkyl or lower alkoxy; a thioether group, in particular a lower alkylthio group such as the methylthio group or ethylthio group as well as an arylthio group, in particular the unsubstituted phenylthio group or a phenylthio group substituted by halogen, e.g. chlorine, by lower alkyl or lower alkoxy. Especially, however, X represents an amino group derived from a primary or secondary organic, preferably aliphatic amine, in particular a monoalkylamino or dialkylamino group such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert. butylamino, dimethylamino, diethylamino, dipropylamino or dibutylamino.

The lower monoand di-alkylamino radicals are preferred on account of the higher solubility of the resulting reactive dyestuffs of Formula III.

In starting materials containing the grouping of Formula II, the lower di-alkylamino radicals are preferred because of the more uniform phosgenization in the synthesis of these starting materials. Furthermore, the radical X may be derived from saturated heterocyclic nitrogen bases such as piperidine or morpholine; or X may represent the radical of a phenylamino or N-lower-alkyl-N- phenylamino group the phenyl radical of which is unsubstituted or substituted by halogen, e.g. chlorine or bromine, or by lower alkyl or lower alkoxy.

Amino dyestuffs of Formula I, into the molecules of which the fiber-reactive grouping according to the invention can be introduced are, for example, amino-anthraquinones such as l-amino-4-(mor p-amino-phenylamino)- or 4-(o-, m or p'-amino-diphenylamino) anthraquinones and their sulfonic acids; aminophthalocyanines such as condensation products of phthalocyanine sulfonic acid chloride with alkylene-diamines or with arylene-diamines which may be sulfonated; and also amino-azo dyestuffs as well as the sulfonic acids thereof. The latter contain acylatable amino groups in the coupling component and/ or in the diazo component.

For instance, aminoazo dyestuffs of the formula are particularly valuable starting materials. In this formula A represents the radical of a diazo component, particularly a benzene diphenyl or naphthalene radical which is unsubstituted or bears a shadeand fastness properties-influencing substitution of the type further described hereinbefore,

B represents the radical of a coupling component,

R and n have the same meanings as in Formula I.

Preferably A and B together contain at least two sulfonic acid groups.

The azo dyestuffs of Formula IV are obtained, for example, by coupling optionally sulfonated acylaminophenyl, acylaminodiphenyl or acylaminonaphthyl diazonium compounds or nitroaryldiazonium compounds, more particularly, for example, by coupling a diazotized acetylamino aniline, 4-acetylamino-4'-amino-1,1'-diphenyl or a nitroaniline which may contain sulfonic acid groups, with conventional coupling components, e.g. with those of the benzene, naphthalene, pyrazole or acyloacetylarylamide series, then saponifying the acylamino group or reducing the nitro group to the amino group. They are also obtained by coupling a diazonium compound with a coupling component containing acylatable amino groups, e.g. with an aminobenzene, aminonaphthalene or aminonaphthol, or also with an aminoaryl pyrazolone or aminoaryl pyrazole imine or with an acyloacetylarylamide or with their sulfonic acids.

Other valuable starting materials are metal-containing aminoazo dyestuffs of the formula A represents a benzene or naphthalene radical which is unsubstituted or bears a shadeand fastness propertiesinfluencing substitution, as described hereinbe-fore,

B represents the radical of a coupling component,

Me represents a heavy metal of the atomic numbers 2- to 29 which can also contain other co-ordinated complex formers,

Y represents oxygen or the COO group, and

R and n have the same meanings as in Formula I.

The bridge members Y and the oxygen atom in Formula V are linked to A and B, respectively, in ortho-position to the azo bridge, -N==N-.

Preferably, the aminoazo dyestuffs of Formula V contain at least two sulfonic acid groups.

Metallized aminoazo dyestuffs of this type are obtained, for example, by coupling optionally sulfonated acylaminophenyl or acylamino-naphthyl or nitrophenyl diazonium compounds which preferably contain a hydroxyl, alkoxy or carboxyl group in the o-position to the diazonium group, with conventional coupling components capable of coupling in a position adjacent to a hydroxyl group, e.g. phenols, naphthols, pyrazolones or acyloacetylarylamides, and also the sulfonic acids of these compounds. They are also obtained by coupling the usual aromatic diazonium compounds, particularly optionally sulfonated o-hydroxyaryl, o-alkoxyaryl or o-carboxyaryl diazonium compounds with coupling components capable of coupling in a position adjacent to a hydroxyl group, which coupling components may contain an acylated amino group, e.g. with an aminonaphthol or acylaminonaphthol, or with an aminonaphthol or acylaminonaphthol sulfonic acid. After the acylamino group has been hydrolyzed or the nitro group has been reduced to the amino group, the aminoazo compounds obtained are converted into heavy metal complexes with agents yielding chromium, cobalt, nickel or copper, if necessary in the presence of an oxidizing agent. To saturate any other co-ordination positions present, the dyestuffs according to the invention can also contain other complex-forming compounds which may have dyestufi character and are bound by -way of the heavy metal, for example, water, certain tertiary amines such as pyridine or another o,o-dihydroxyor o-hydroxy-o'-carboxyazo dyestuff.

Compounds usable according to the invention which introduce the radical of Formula II, above, into the dyestuff starting materials of Formula I are mainly the carbamic acid chlorides of the formula wherein wherein Hal and X have the same meanings as in Formula II.

The carbamic acid chlorides of Formula VI are obtained by known processes, in particular by reacting halogen-amino-s-triazines compounds of the formula N (lower alkyl) (VII) in which X and Hal have the same meanings as in Formula II,

with phosgene in an inert organic solvent. Suitable solvents are, e.g. optionally halogenated or nitrated aromatic hydrocarbons such as toluene, chlorobenzene or nitrobenzene.

The reaction of an amino dyestuff of Formula I with the acylating agent introducing the radical of Formula II, preferably a compound of Formula VI, is advantageously performed in aqueous solution, optionally in the presence of inert organic solvents, e.g. lower alkanols, lower aliphatic ketones or lower fatty acid amides, if necessary in the presence of buffer salts or tertiary nitrogen bases such as dialkyl anilines as acid binding agents. To prevent a premature exchange of substituents which can be split off, the reaction is performed with care under mild conditions, preferably at a pH of 4 to 8 and at as low temperatures as possible. Mild conditions are also indicated for the isolation and drying of the reaction products.

Reactive dyestuffs of Formula III are also obtained by a modified process by forming them from dyestulf components which contain at least one radical of Formula II bound by way of an amino group This method is particularly suitable for the production of azo dyestuffs and comprises coupling an aromatic diazonium compound with a coupling component, at least one of which contains the characteristic fiber-reactive acylamino group according to the invention.

For example, a diazonium compound of the formula Hal(l3 :-1y c0-1 1-A1N2 N N (lower alkyl) X (VIII) wherein A represents a benzene, diphenyl or naphthalene radical or an azo dyestuff radical, which may have further shadeand fastness properties-influencing substitution as described hereinbefore,

R has the same meaning as in Formula I, and

Hal and X have the same meanings as in Formula II,

is coupled with a coupling component BH to form an azo dyestuff of the formula A has the same meaning as in Formula VIII, and B represents the radical of a coupling component;

if desired, metallizable dyestuffs thus obtained are then reacted with agents introducing a complex-forming heavy metal.

Diazonium compounds of Formula VIII used in this process are derived from optionally sulfonated arylenediamines, such as por m-phenylenediamine sulfonic acid or 2,6-naphthylene-diamine-4,8-disulfonic acid.

Components to be coupled therewith are those conventional in azo dyestuffs, for example, those of the benzene series such as phenols or anilines, of the naphthalene series such as optionally sulfonated naphthols, naphthylamines or phenyland acyl-aminonaphthols, furthermore, pyrazolones, pyrazole imines or acryloacetylarylamides.

A further method of performing the process for the production of reactive dyestuffs of Formula III comprises reacting an aryl diazonium compound with a coupling component of the formula R HBI ICO N(lwer alkyl) wherein R has the same meaning as in Formula -I, Hal and X have those given in Formula II and B represents the radical of an azo dyestuff-forming coupling component,

to produce a dyestuff of the formula wherein R A1N=NBI\'IC 0 Ifi- (lower alkyl) 3 or azo dyestuff series which may be further substituted, and, if desired, converting a dyestuff thus obtained which possesses metallizable substituents in A and B, to a heavy metal complex thereof, with agents giving off heavy metal.

Diazotized aromatic amines usual in azo dyestuffs are used in this process as diazonium compounds, for example, optionally sulfonated phenyl, diphenyl, naphthyl or azo dyestuff diazonium compounds. The latter are especially benzene-azo-benzene-diazonium, benzene-azonaphthalene diazonium, or naphthalene azo benzenediazonium compounds.

In Formula X, B, the radical of the coupling component of the dyestuff of Formula XI, represents, for example, the radical of an aminonaphthol sulfonic acid such as the radical of a 1-amino-6- or -7-hydroxynaphthalene sulfonic acid, of l-amino-8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid, of 2-amino-8-hydroxynaphthalene 6- sulfonic acid, or the radical of an optionally sulfonated aminoaryl pyrazolone or pyrazole imine or of an acylacetylarylamide.

Azo dyestuffs containing two radicals of Formula II are obtained, for example, by coupling a diazonium compound of Formula VIII with a coupling component of Formula X.

The coupling is performed in every case in a weakly acid to weakly alkaline medium by the usual methods.

Both the coupling and the metallization must be performed under mild conditions, i.e. high pH values and temperatures should be avoided.

The dyestuffs obtained can be stabilized with buffer substances, for example with mixtures of primary and secondary alkali phosphates or with alkali metal salts of sulfonated tertiary aromatic amines, that is, for example, with the sodium salt of N,N-dimethylaniline-3-sulf0nic acid.

The preferred dyestuffs of Formula III contain water solubilizing, salt-forming groups and are suitable for the dyeing of natural and synthetic polyamide fibers containing amino groups. An after-treatment of the dyeing with acid-binding agents such as ammonia or hexamethylenetetramine improves the wet fastness properties, especially of dyeings on wool.

Water soluble reactive dyestuffs according to the invention which correspond to Formula 'II and contain advantageously two to five sulfonic acid groups are mainly used, however, for the dyeing and printing of textile fibers containing hydroxyl groups, particularly for natural or regenerated cellulose fibers. Dyeings and prints are obtained which are distinguished by excellent wet fastness properties and good fastness to light by impregnating the textiles with aqueous dyestuff solutions or printing them with thickened dyestuff solutions, drying the impregnated material and treating with acid binding agents, optionally with heating or steaming, and then thoroughly rinsing and soapmg.

The dyestuffs according to the invention are also suitable for the dyeing of fibers containing hydroxyl groups by the exhaustion process. During or after the dyeing process which, advantageously, is promoted by the addition of neutral salts such as sodium sulfate or sodium chloride, the dyestuff is fixed by treatment with acid binding agents. A particularly simple dyeing process consists in adding the total amount of the neutral salts which promote exhaustion and adding the acid binding agent to the dyebath from the very beginning, introducing the goods to be dyed at low temperatures (25-40 C.) into the bath, heating the bath gradually to a temperature, depending on the aforementioned starting temperature, in the range of from 40 to C., and continuing treatment at the latter temperature until the fixation of the dyestulf is completed. In this way, dyeings having excellent wet fastness properties and good fastness to light are obtained.

Reactive dyestuffs of \Formula HI wherein Hal is chlorine are fixed at room temperature (about 20 C.) when the bath is strongly alkaline (pH above 11) or, preferably, at elevated temperatures (60 to C.) at lower pH (about 9 to 11) and those in which Hal represents fluorine are fixed under milder conditions, e.g. at lower temperatures (20 to 30 C.) and/or lower pH (8-11), or correspondingly shorter time.

Wet fastness properties shown by the dyestuffs according to the first and also by those of the second aspect of this invention, described in detail hereinafter, are, in particular, wash fastness, fastness to water, to sea water, to perspiration, and, in the case of wool dyeings, also fastness to milling and potting. These wet fastness properties are also found in wool dyeings of stronger shades (e.g. standard depths 2 to 5).

Moreover, the yield rate of fixed dyestuff to unfixed dyestuff portion on wool is very favorable in the case of dyestuffs of the first as Well as of the second aspect of the invention.

In the dyeing of cotton and the like cellulose fibers, the unfixed portion of these dyestuffs remaining on the fibers after fixation, can be very readily removed by washing with hot water or by soaping. Wool dyeings are distinguished by level strike of these dyestuffs irrespective of differences in the type of wool, which levels strike is assured especially by the use of anionic or non-ionogenic dyestuff carriers or mixtures of such carriers.

Preferably sodium or potassium bicarbonate, sodium or potassium carbonates, sodium metasilicate, trisodium phosphate or sodium hydroxide solution, or the sodium or potassium salt of trichloroacetic acid are used as acid binding agents. In addition the dye liquor or printing paste can contain further additives, for example salts such as sodium sulfate or chloride already mentioned, or auxiliaries such as acid amides, e.g. urea or additives which prevent reduction such as nitrobenzene sulfonic acid, and also additives which accelerate the reaction, such as tertiary amines, e.g. trimethylamine or 1,4-diaza-bicyclo-(2,2,2)-octane.

Reactive dyestuffs according to the invention which correspond to Formula III and which contain no sulfonic acid group are preferably used in fine aqueous dispersion for the dyeing of hydrophobic fibers, in particular for the dyeing of synthetic polyamide fibers such as nylon.

Further details can be seen from the following nonlimitative examples of this aspect of the invention. Where otherwise expressly stated, parts and percentages are given by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams (g) to milliliters (mL).

EXAMPLE 1 CH 02H; I 01 18.8 parts of 1,3-diaminobenzene-4-sulphonic acid are dissolved in 400 parts of water with the addition of sodium carbonate to give a pH of 4.0-4.5, and the solution is cooled to -5". 27.7 parts of 2-ethylamino-4-N- chloroformyl-ethylamino-6-chloro-s-triazine dissolved in 100 parts of acetone are added dropwise at this temperature within 15 minutes, the pH of the reaction mixture being maintained at 4.0-4.5 by the simultaneous addition of sodium carbonate solution. As soon as the reaction is completed, 25 parts of aqueous 30% hydrochloric acid are added and diazotisation is performed with 6.9 parts of sodium nitrite at 0-5 The suspension of the diazonium compound is poured into a solution of the sodium salt of 28.9 parts of l-(2-chloro- '-sulphophenyl)-3-rnethyl-5-pyrazolone in 200 parts of water and 40 parts of sodium acetate. On completion of the couplings, the new dyestuff is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 40-50. It is a yellow powder which dissolves in water with a greenish yellow colour.

The new dyestufi dyes cotton, staple fibre, jute, ramie, hemp, wool, silk and nylon by the processes usual for reactive dyestufis in pure yellow shades which are fast to wet and light.

Dyestuffs having similar properties are obtained when, instead of the 1-(2'-chloro-5'-sulfophenyl)-3-methyl-5- pyrazolone, an equivalent amount of the coupling components given in the following Table 1 are used.

naphthalene3,6-disulion1c acid.

10 EXAMPLE 9 O H NH-C2H 42.1 parts of the aminomonoaza dyestufii of the formula (produced by diazotizing 2-aminonaphthalene-4,8-disulfonic acid and coupling the diazonium compound with l-amino-B-methylbenzene in the presence of alkali metal salts of fatty acids) are dissolved inthe form of the sodium salt in 400 parts of water. 29.1 parts of 2-ethylamino-4-N-chloroformyl-ethylamino -6 chloro-s-triazine dissolved in parts of acetone are added dropwise at 20-25 within 1 hour, the pH of the reaction mixture being kept at 6.5-7.0 by the simultaneous addition of sodium carbonate solution. As soon as no more free amino groups can be traced, the reaction product is precipitated by the addition of sodium chloride, filtered off and washed with dilute sodium chloride solution. The new dyestuff is dried in vacuo at 40-50". It is a yellow powder which dissolves in water with a yellow color. It dyes cellulose and polyamide fibers by the processes usual for reactive dyestuffs in pure yellow shades which have good fastness to wet and light.

Other azo dyestuffs having similar properties are obtained by reacting equivalent amounts of the aminoazo dyestufis given in the following Table 2, in accordance with Example 9 with Shade on cellulose fibers Yellow.

Example N o. React-ant a, b, c, d, e, f

Aminoazo dyestufi 10 2-aminonaphthalene-5,7-

disulfonic acid aniline.

11 2-aminonaphthalene-4,&

disulfonic acid 2- methoxy-5-methylaniline.

12 2-aminonaphthalene-4,6,8-

trisulfonic acid aniline.

13 2-aminonaphthalene-4,6,8-

trisulfonic acid 3- methyl-l-aminobenzene aniline 14 4-aminoazobenzene-3,4- disulfonic acid 3- methyl-l-aminobenzene.

15- 2aminonaphthalene-4,8-

disulionic acid N- methylaniline.

16 l-aminobenzene-2A-disulionic acid 1-aminonaphthalene-fi'sulfonic acid A l-methyl-B- aminobenzene.

17 1-aminobenzene-2,5-disnlionic acid m-aminophenyl urea.

a, b, c, d, e, f Do.

a, b, c, d, e, i Do.

a, b, c, d, e, 1' Orange.

a, b, c, d, e, t Do.

a, b, c, d, e, 1 Yellow.

a, b, c, d, e, f Orange.

a, b, c ,d, e, 1. Yellow.

1 1 EXAMPLE 18 50.3 parts of the amino azo dyestuff of the formula (produced by coupling diazotized 2 amino-4-acetylaminobenzene-l-sulfonic acid with 2 hydroxynaphthalcue-6,8 disulfonic acid in an alkaline medium and saponifying the acetylamino group with sodium hydroxide solution, in accordance with the procedure described by Fierz-David and Blangey in Farbenchemie, 8th edition, page 283 et seq.) are dissolved, in the form of the sodium salt, in 800 parts of water with a neutral reaction. 30.6 parts of Z-dimethylamino-4-N-chloroformyl-n-butylamino-6-cl1loro-s-triazine dissolved in 100 parts of acetone are added at 1520 the pH of the reaction mixture being kept at 5-5.5 by the addition dropvvise of sodium carbonate solution. As soon as no more diazotizable amino groups can be traced, the dyestutf is completely precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 60-70". It dissolves easily in water with an orange color and dyes polyamide and cellulose fibers by the processes usual for reactive dyestuffs in yellowish orange shades.

By reacting the aminoazo dyestuffs listed in the following Table 3 according to the procedure described in Example 18 with, in each case,

(a) 2-dimethylamino-4-N-chloroformyl-n-butylamino-6- chloro-s-triazine or with equivalent parts of (b) 2-methoxy-4-N-chloroformyl-ethylamino-6-chloros-triazine,

(c) Z-phenoxy-4-N-chloroformyl-methylamino-6- chloro-s-triazine,

(d) 2-morpholino-4-N-chloroformyl-methylamino-6- bromo-s-triazine,

(e) 2-(4-methoxy-phenoxy)-4-N-chloroformyl-ethylamino-6-chloro-s-triazine,

(f) 2-(4'-chlorophenylamino)-4-N-chloroformyl-methylamino-6-chloro-s-triazine and (g) Z-dimethylamino-4-N-chloroformyl-methylamino- 6-chloro-s-triazine,

TABLE 3 Shade on cellulose fibers Example No. (a-g) Aminoazo dyestuffs 19 2-amino-4-nitrobenzcne sulphonic acid Red.

1-acetylamino'8-hydroxynaphthalener3,6- disulphonic acid, reduced.

2-amino 4-nitrobenzene sulphonic acid l-benzoylamino-8hydroxynaphthalene- 3,6-disulphonic acid, reduced.

2-emlno-4-acetylaminobenzene snlphonic acid 1-hydroxynaphthalene-3,& disulphenic acid, saponified. 2-amin04-acetylaminobenzene sulphonic acid 1-hydroxynaphthalene-4,6- disulphonic acid, saponified. 1-aminobenZene-2,5-disulphonic acid alkaline 2-amino-5-hydroxynaphthalenefl-sulphonic acid. 2-aminonaphthalene-l,fi-disulphonic acid kaline 2-mcthylamino-5-hydroxynaphthalene-7-sulphonic acid.

l-aminobenZene-2,4-disulphonic acid l-(3-aminobenzoylamino)-8-hydroxynaphthalene-3,fi-disulphonic acid.

2-amino-4-acetylaminobenzene sulphonic acid 2-aminonaphthalene-5,7-disulphonic acid, saponiilcd.

2-arninOA-acetylaminQbenZene sulphonic acid l-(3-sulpl1ophenyl)-3-methyl-5- pyrazolonc, sepom'fied.

2-amino-5-nitrobenzene sulphonic acid 1-(3'-sulphophenyl)-3-methyl-5-pyrazole imine, reduced.

29 l-amino-3-nitro-6-ethylbenzene l-hydroxy naphthalene-3,6-disulfonie acid, reduced.

30 l-amino-3-N-methylsulfamylbenzene l-amino-8-hydroxynaphthalene-3,6- disulfonic acid.

31 l-aminebenZene-S-N-(v-hydroxypropyb- N-methylsulionamide l-aminoS- hydroxynaphthalene-3,6-disulfonie acid.

32 4-amino-3-earboxy-benzene-sulionlc acid 2-amino-6-hydroxynaphthalcue-7- sultonic acid.

l-aminobenzene-ii-N-(B-hydroxyethyl)- N-methylsulionamide 1-amino-8- hydroxynaphthalenet,fi-disulionic acid.

34 3-amino-4-ethoxybenzene-sulfonic acid 2-amino-5-hydroxynaphthalene-7- sulionic acid.

35 1-aminobenzene-3'N-(fl-sulfoethyl) -N- methylsulfonamide l-amino-S-hydroxynaphthalene-3,6-disul1onic acid.

36 Z-aminonaphthalene-4,6,8-trisu1ionic acid 1-(4-aminophenyl)-3-methyl-5- pyrazolone.

37 1-amino 3-N,N-bis-('y-hydroxypropyD- suliemyl-benzene l-amino-S-hydroxynaphthalene-3,G-disulfonic acid.

38 2,3-diamino-diphenyl-l,l-disulfimide l-amino'8-hydroxynaphthelene-3fidisulfonic acid.

39 2aminenaphthalene-1,5,7-trisulfonic acid 2-arnino-5-hydroxynaphthalene-7-sulionic acid 1-amino-3-methylbenzene.

40 z-arninoi-nitrobenzcne sulionic acid l-benzoylamino-B-hydroxynaphthalene- 4,6-disulionic acid, reduced.

20 Red.

Orange.

Red-orange.

Orange.

Reddish orange.

Red.

Orange.

Yellow.

Reddish orange.

Red.

Red:

Orange.

33 Red.

Orange.

Red.

Yellow.

Red.

Red.

Red.

Red.

As used in the above Table 3 and subsequent tables means that the coupling was carried out in a conventional manner at a pH above 7, saponified means that the coupled product was treated as described in Exam- 13 14 pic 18, supra, and reduced means that the coupling It dyes cotton, staple fiber, jute, ramie, hemp, wool, silk product was treated as described in Example 40h, infra. and nylon by the processes usual for reactive dyestuffs in EXAMPLE 40h pure ruby red shades which are wet fast.

so n H(|) I |IHCO- Cl N=N 62.2 parts of the sodium salt of the aminoazo dyestuff Further metal-containing aminoazo dyestufis are given of the formula in the following Table 4 which are reacted as described in this example with 803E H0 (a) Z-methylamino-4-N-chloroformyl-methylamino- -N=N l 6-chloro-s-triazine or with equivalent parts of (b) 2-ethylamino4-N-chloroformyl-ethylamino-6- IIqHZ Hogs SOQH chloro-s-trlazme,

(c) 2-ethoxy-4-N-chloroformyl-methylamino-6- chloro-s-triazine,

(obtained by coupling diazotized 2-amino-4-nitrobenzene (d) 2- h lthio.4-N. h1 fo b th l ino-6.. sulfonic acid with 1-benzoylamino-8-hydroxynapthalenehl -t i i 3,6-disulfonic acid in a neutral medium and reducing the 2 l i -4 N- hl f myleb t lamino-6- nitroazo dyestutf with sodium sulfide in alkaline medium h1 -1; i i d of pH about 10-12) are dissolved in 500 parts of water. (f) 2-(4'- h 1 h 1 hi )-4-N. h1 f At 15-20", 29.0 parts of 2-ethylamino-4-N-chloroformylth 1 i -6- hl -t i i ethylamino-6-chloro-s-triazine dissolved in 100 parts of acetoneare added dropwise, the pH of the reaction if i 2 8 shades. of q i wlth i endfproducts solution being kept at 5.0-5.5 by the addition of sodium on Ce u 086 ers are gwen m 6 ast 00 um 0 Table carbonate solution. As soon as no more free amino groups can be detected, the dyestulf is completely precipitated by the addition of sodium chloride, filtered off and dried in TABLE 4 vacuo at 60-70. It dissolves easily in water with a red E 1 shfiidle on r xamp e co n ose color and dyes celhjflose and po lyamlde fibers by proc 30 No. (a-f) Metal-containing amlnoazo dyestufis fibres esses usual for reactive dyestuffs in pure red shades.

42 2-amin0-1-hydroxybenzeneA,6-disulphonic Violet. EXAMPLE 41 alkallne acid Lamino-8- hydroxynaplithalenekfi-disnlphonic acid, copper comp ex. 43 Z-afimg-l-hydroxyb61116911846111131101110 acid Bordeaux.

a a ne H033 2-amino-8-hydroxynaphthalene- CH3 fi-sulphonic acid, copper complex.

N 44 G-nitro-l-amino-2-hydroxynaphthalene-4- Black. no s- NH- oo-N NEE-CH alkaline sulphonic acid 2-am1no-5- hydroxynaphthalene-7-sulphonic acid, 30 B 45 chromium complex 1:2.

\/ alkaline Do.

| 45 4-nltro2amino-1-hydroxybenzene 1- C1 amino-8ehydroxynaphthalene-3,6-

disulphonic acid, chromium com fifxl 1:2. Bl k a a lne ac -min-1-hd b tzflflfpafits fof thel copper containing ammomonazo dye- 4 3313?;25-hy05tgiaifilai3fi8??? 1 brown rm sup omcac ,co a comp ex Stu o t e O u a 47 2-amino-4-acety1amino-l-hydroxybenzene-G- Reddish alkaline navy 0 C o sulphonic acid I-aminc-S- blue.

u I hydroxynaphalene-ZAdisulphonic acid, 5 48 2 eoppercomplex, sapojrnfiieg. b 6 N ammo ace y anunoy roxy enzene avy H 0 3S -N-N 5 5 alkaline blue.

ne une en...

- y roxynap aenesup oncac H038 NH? copper complex, saponified. 40- fi-nitro-l-amino2hydroxynaphthalene-4- Blue. so H alkaline 3 sulphomc acld 1-amino-8- hyadroxgnaphthaleneilA-disulphonic acid, re uce copper comp ex. (obtained by couphng diazotlsed Z-anuno-I-hydroxy- 50 2-mniinfi-fi-iacetyglamino-lihydroxybenzene-i- Ruby sup oncaci red. benzene dlsulphom? i Wlth 2 m 5 hydroxy hydroxynaphthalone-4,6-disulphonic acid, naphthalene-7-sulphonlc acld in an alkaline medium and copper complex, s aponified. treating the aminomonoazo dyestuff obtained with an 51 qg ggggg ggg fi tgtf $3833 agent giving off copper) are dissolved, in the form of the disulphopherllyl)-3-metgyli5-pyrazolone,

a o copper comp ex, sapon e sodium salt, 1n 1000 parts of water. At 0 10 a solution 52 Lhydmxyafimmomethylsmfonylbemene 1mm of 27.6 parts of Z-methylammo-4-N-chloroformyl-methylg-amino-S-hydroxynaphthalene-3,6-

disulp onic acid, copper complex. ammo 6 ch10) s tnazm? m 15 0 i of f q 15 added 53 3-amino-4hydroxy-benzolsu1fonic acldfi Yellow. and the pH of the reaction solution 18 maintained at 5.5- N-(3-arninophenyl) acetoacetlc acid amide 1:2-coba1t complex. 6.0 by the addition of sodium carbonate solutlon. As soon 54 ,4 j br ob nzol 1- Violet. as no more free ammo groups can be traced, the new dyeamino-S-hydroxynaphthalene-3,6-d.isulfonic acid, copper complex. stufi s completely precipitated by the addition of sodium 55 mydmxwfamiuo bemenej N (fl Ruby. chloride, filtered off and dried 1n vacuo at 40-50 It is methoxyethyl)-N-amylsulionamide-- 2 a dark powder which dissolves in water with a. ruby red amms'hydmxymphthalenee'i,fi'dlsulmnic acid, co er com lex. color; pp p 56.9 parts of l-amino-4-(4-aminophenylamino)-anthraquinone-2,2',7-trisulphonic acid (obtained by sulphona- (d) Z-N-methyl-N-(4'-chloropheny1amino) -4-N- tion of l-arnino-4-(4'-aminophenylamino)-anthraquinone- 2,7-disulphonic acid in 30% oleum) are dissolved, in the form of the sodium salt, in 1000 parts of water. A solution of 27.7 parts of 2-ethylamino-4-N-chloroformyl-ethylamino-6-chloro-s-triazine in 100 parts of acetone is added to this solution dropwise at 20-25 and the pH is maintained at 5.0-5.5 by the simultaneous addition of aqueous sodium carbonate solution. On completion of the reaction, the new dyestuff of the above formula is precipitated by the addition of sodium chloride, filtered olf, washed with 16 aqueous sodium chloride solution and dried in vacuo at 40-50. It dissolves in water with a blue color and dyes cotton, staple fiber, jute, ramie, hemp, wool, silk and nylon by the processes usual for reactive dyestuffs in wet fast blue shades.

Other aminoanthraquinone dyestuflfs listed in the following Table 5 are condensed as described in Example 56 with (a) 2-ethylamino-4-N-chloroformyl-ethylamino-6-chloros-triazine or with equivalent parts of (b) 2-methylthio-4-N-chloroformyl-methylamino-G- chloro-s-triazine, (c) 2-diethylamino-4-N-chloroformyl-methylamino-6- chloro-s-triazine,

chloroformyl-butylamino-6-chloro-s-triazine, (e) Z-N-methyl-N-(4'-ethoxyphenylamino)-4-N- chloroformyl-methylamino-6-chloro-s-triazine, and (f) 2-phenylamino-4-N-chloroformyl-ethylamino-6- chloro-s-triazine,

respectively. The shade of the cellulose dyeings obtained with the resulting reactive dyestuffs is given in the last column of Table 5.

TABLE 5 Shade on Example cellulose No. Aminoanthraquinone dyestuif fibres 57 (N) 11TH: Blue.

A -SO H NHz Y 1 3 0 NH- -S03H 58 (H) IIIHa D0.

H038 SO3H II I NH- -SO3H l NH5 59 fl) 11TH: DO.

Ho,s SO H Y 0 NH- NH2 OaH 60- f) IIIH: DO.

@ SO H O NH- SO3H 17 18 EXAMPLE 62 TABLE 6 57.6 parts of copper phthalocyanine tetrasulphonic acid g ample Sl ige on O. chlorlde are slurned 1n 500 parts of water and 390 parts (.14) Ammwhthamyamne dyestufl of we parts of m-ammoacetamlide are stirred 1n and the pH is adjusted to 7 by the addition of aqueous 5 63 :L gfg ammonia solution. The temperature is allowed to rise CuPc slowly to 40-50, the pH of the suspension being main- TS02 NH(CH)2 NH2 tained at 7.0-7.5 by the dropwise addition of ammonia solution. As soon as no more primary amine can be traced, 64 lworNfim 270 parts of 30% hydrochloric acid are added and the 10 CuPc mixture is heated for 3 hours at 85-90. In this way the T Q acetyl amino group is saponified.

The amino-phthalocyanine dyestufi' of the formula r EXAMPLE 65 solrr on P -s 0:4NH- l I am N /CH: Nn2so2 u (SO Na) L 2 ll; CH; wherein Pc represents the phthalocyanine structure 5033 $03K 51 23.9 parts of 2 amino 8 hydroxynaphthalene-G- sulphonic acid are dissolved in 400 parts of 1520 warm water and the pH is adjusted to 6.5 with sodium hydroxide solution. A solution of 30.6 parts of Z-N-methyl-N-ethylamino 4-N-chloroformyl-ethylamino-6-chloro-s-triazine in 100 parts of acetone is added dropwise to this solution within 15 minutes and the pH of the reacting mixture is kept at 4.5-5.5 by the addition of sodium carbonate solution. When no more diazotisable amino groups can be traced, parts of sodium bicarbonate are added to the solution and then a solution of 30.3 parts of diazotised 2 aminonaphthalene 1,5 disulphonic acid is poured in. As soon as the coupling is completed sodium chloride is so obtained.

This dyestulf is then isolated by filtration, again slurried in 1000 parts of 0-5 cold water and the pH of the sus- 2 pension is adjusted to 8.0 with dilute sodium hydroxide solution. A solution of 27.7 parts of 2-ethylamino-4-N- chloroformyl-ethylamino-6-chloro-s-triazine in 100 parts of acetone is poured into this suspension. Condensation is performed at 15-20 While stirring well and the hydro- 3 chloric acid liberated is neutralised by the dropwise addition of dilute sodium carbonate solution. On completion of the reaction, the new dyestufi is completely salted out, filtered oh and dried in vacuo at 50-60. It corresponds to the formula is added to the reaction mixture, the precipitated dvestutf SO -NH CQHE NH so cum I 30 N) l N l. J a NH00N-f TNH-C H;

wherein is filtered off and washed with sodium chloride solution. PC re resents the phthalocyanine Structure After drying at 60-70, a red powder is obtained which p dissolves easily in water with a red colour. It yf Cellulose polyamlde fibres 111 Well fast, pure If cotton or staple fibre is dyed or printed by the lufquolse b1l 1e Shadesprocesses usual for reactive dyestuffs, with this dyestuif other ammo'phthalocyanlne dyestuffs Whlch g fi then red dyeings or prints are obtained which have very in the following Table 6, are condensed as described in d properties Example 62 with Other dyestuifs having similar properties are obtained (a) 2 ethy1amino 4 N chloroformyl ethylamino 6 if the coupling components containing acylatable amino chlorwsfiiazine, with equivalent Parts of groups given in the following table are condensed as de- (b) 2-piperidino-4-N-chloroformyl-methylamino-6- Scnbed 111 Example 65 Wlth chloros-triazine,

a) 2 N methyl N ethylammo 4 N chlorol ifiggi gg il N-chlomformyl ethylammo 6 formylethylamino-6-chloro-s-triazine,

3 (dghgiibsuggifizo-4-N-chloroformyl-methylam1no-6- or with equivalent parts of 7 a '-methylphenylammo):4-N-ch1oroformy1- (b) 2-ethylamino-4-N-chloroformyl-ethylamino-G-fiuoromethylammo-6chloro-s-tr1az1ne, and Mriazine, (f) Z-N-methyl-N-(4'-methylphenylammo)-4 -N- ch10roformyl'methylammo'6'bromo's'tnazme and coupled with the diazo components also given in respectively. the Table 7.

TABLE 7 Example Shade of N0. (a-b) Diazo component Coupling components containing acylatable amino groups cotton 66 l-aminobenzene-2,5-disulphonie acid l-amino-8-hydroxynaphtha1ene-3,6-disu1phonie acid Red. 67 Z-aminonaphthalene-l,5-disulph0ni0 acid n 131m:1 is

re 68 l-aminobenzene-Z-sulphordc acid 1-amin0-8=hydroxynaphthalene-4,6-disu1phonic acid Red. 69 l-aminobenzeneZA-disulphonic acid 1-(4-aminophenyl)-3-methyl-5-pyrazo1one Yellow. 70 l-aminobenzene-Z,5-disulphonlc acid 2 amino5-hydroxynaphthalene-7-sulphonlc acid Orange. 71 4-aminoazobenzene-3,4-disulphonic acid.-- 2-methylamino-4-hydroxynaphthalene-7-sulphonie a d Scarlet. 72 2-aminonaphthalene-1,fi-disulphonic acid.-. l-amiuo-8 hydroxynaphthalene-4,6-d1sulphonic acid Blue is red.

EXAMPLE 73 potassium fluoride in dimethyl formamide to form 2,4-bis- CH3 ethylamino-6-fiuoro-s-triazine and treating the latter ac- N 2 5 I 01 cording to known methods with phosgene in toluene. F S0311 By padding cotton at room temperature with a 2% J aqueous solution of this dyestuff which also contains N arts of sodium carbonate and 50 arts of sodium sul- N c l P I H S a phate per litre, rolling up the impregnated goods, wrap- NHCZHI ping in a plastic cover and keeping for 4 hours at 30 18.8 parts of 1,3-diaminobenzene-4-sulphonic acid are gfi g g :fifgiifiifiigg11221:? o d i st t dissolved in 400 parts of water and the pH is adjusted 1O zvashin i 1 ht y g a ness 0 to 4.0-4.5 with sodium carbonate. 26 parts of 2-ethyl- D esgtuffs similar r0 erties ar obtain d amino-4-N-chloroformyl-ethylamino 6 fluoro-s-triazine accoirldance with recedig E 16 i 25 dissolved in 100 parts of acetone and an aqueous sodium th b g p ens1.g carbonate solution are added simultaneously to this solue lammo enzene omc acl S gwen tion within 15 minutes at in such a way that the 15 column II of the following Table 8 with equivalent parts pH of the reaction mixture remains between 4.0 and 4.5. of the acylatlflg agents Elven colufnn of said table; o completion f h reaction 25 parts f hydro the condensation products are then d1azot1zed and the rechloric acid are added to the condensation product which Sultmg 1131011111111 P are finally Coupled Wlth the is then diazotised at 0-5 with 6.9 parts of sodium nitrite. coupllng components listed in column IV. The shade on The suspension of the diazonium compound is poured 2O cellulose fibers obtained with thefinal products is given into a solution of the sodium salt of 28.9 parts of 1-(2'- in the last column of Table 8.

TABLE 8 II III IV V Shade on Example Diaminobenzene sulphonic acid cellulose No. compound Acylating agent; Coupling component fibres 74 1,3-diaminobenzene-4-sulphonic acid.. N 1-(2,5'-disulphophcnyl)-3-mcthyl-5- Yellow.

Ff fi-NHCzHs pyrazolone.

III-C001 01H;

7 do Sameasabove....:::::::::.:.:.:;: 1-(2',5'-dichloro-4-sulphophenyl)-3- Do.-

methyl-B-pyrazolone. 76 do A n 4 I 1-(3-sulphophenyl)-3-methyl-5- Do.

pyrazolone. 77 do do 1-[5,7-disulph0naphthyl-(2)]-3-methyl-5- Do.

pyrazolone. 7 do r do 1-[4',8-disulph0naphthyl-(2)]-3- Do.

methyl-5-pyrazolone. 79 do do n 1-(4-sulphopheny1)-5-pyrazolonc-3- Do.

carboxylic acid.

80 l,4-dlaminobenzene-S-sulphonic acid do do I Do. lAdiaminobenzcne-3-sult0nic acid 2-dimethylrmiinot-N-chlorofonnyl- 1-(4-sulfophenyl)-5-pyrazolone Do.

metiiylamino-G-fiuoros-triazine. carboxylic acid. 82 1,3-diaminobenzene-4-sultonic acid do do Do. 83 do 2-propylamino-4-N-chloroformylmethyl- 1-(2,5-disulfophenyi)-3-methyl-5- Do.

aminofi-fluoro-s-triazine. pyrazolone. 84 o 2-ethylthio-4Nchloroformylbutylamino- 1-(2,5-dichloro-4-suliophcny1)-3-mcthyl- Do.

G-fiuoro-s-triazine. fi-pyrazolone. 85 do 2-methoxy-4N-chloroformylmethyi- 1-(3-sulf0phcnyl)-3-mcthyl-5-pyraz0lonc. Do.

amino-B-fluoro-s-triazine. 86 do 2-phenoxy-4-N-chioroformylmethyi- 1-[5,7-disulfonaphthyl-(Z)]-3-mcthyl-5- Do.

amino-G-fluoro-s-triazine. pyrazolone. 87 do 2-cthoxy-4-N-chloroiormylethylamino-6- 1-[4',8-disulfonaphthyl-(2)]-3-mcthyl-5- Do.

fluoro-s-triazine. pyrazolone. 88 1,3-diaminobenzcnei-suifonic acid 2-amylamin0-4-N-chloroformylmethyl- 1-(4-sulfopheny1)-5-pyrazolonc-3- D0.

amino-6-fiuoro-s-triazine. carboxylic acid. 89 do 2-dibutylamino-4-N-chloroformylmcthyl- 1-(2-iluoro-5-sul1'ophenyl)-3-mcthyl-5- D0.

amino-G-tluoro-s-triazine. pyrazolone. 90 do 2-phenylamino-4-N-chloroformylmethyll-chloroacetylamino-8-hydroxynaphtha- Rod.

amino-G-fiuoro-s-triazine. lone-3,6-disult0nic acid. 91 do 2-N-methyl-N-ethylamino-4-N-chloro-1 2-(B-bromopropionylamiuo)-8-hydroxy- Scarlet.

formylrnethylamino-fi-fluoro-s-triazine. I naphthalene-3,(i-disullonic acid.

chloro-5'-sulphophenyl)-3-methyl-5 pyrazolone in 200 EXAMPLE 92 parts of water and 4 parts of sodium acetate. As soon as the coupling is complete the pH of the dyestufi solution 60 303K CH3 is raised to 7.0 and the new dyestufi is precipitated by the l N addition of sodium chloride. Also 19.5 parts of a mixture NHLO-N' W of anhydrous primary potassium phosphate and anhy- E N drous secondary sodium phosphate in a weight ratio of H3 1.8:1.0 are added. 65 I SOQH NHCH The mixture is stirred for 1 hour and the precipitate is filtered off, washed, and mixed with 11.7 parts of the mixture of anhydrous primary potassium phosphate and anhydrous secondary sodium phosphate mentioned above and dried in vacuo at a temperature under 45'.

The monoazo dyestuif so obtained is a yellow powder which dissolves in water with a greenish yellow colour.

The 2 ethylamino 4 N chloroformyl-ethylamino- 6 fiuoro-s-triazine used as starting material is obtained by reacting 2,4 bis-ethylamino-6-chloro-s-triazine with 42.1 parts of the sodium salt of the aminoazo dyestuft' obtained by coupling of diazotized Z-aminonaphthalene- 4,8-disulfonic acid with l-amino-3-methylbenzene are dissolved in 400 parts of water and the solution is cooled to 0-5. 24.2 parts of 2 methylamino-4-N-chloroformylmethylamino-6-fiuoro-s-triazine dissolved in parts of acetone are added dropwise to the solution within 30 minutes at this temperature and the pH of the reaction mixture is kept at 6.5-7.0 by the simultaneous addition of sodium carbonate solution. As soon as no more free amino groups can be traced, a solution of 40 parts of a mixture of primary potassium phosphate and secondary sodium phosphate (weight ratio 1.821) in 200 parts of water is added to the reaction mixture. The new dyestuff is precipitated by the addition of sodium chloride, after stirring for 30 minutes it is filtered oil? and .washed with dilute sodium chloride solution. The filter residue is mixed with 12 parts of a mixture of anhydrous primary potassium phosphate and anhydrous secondary sodium phosphate (ratio 1.23:1) and dried in vacuo at a temperature under 45 After drying, the dyestulf is a yellow powder which dissolves in water with a yellow color.

4 parts of the new dyestulf are dissolved in 1000 parts of water and parts of sodium carbonate are added. 100 parts of cotton are entered at 20 and the bath is heated to 40 within minutes, 80 parts of sodium chloride are added to the solution and the goods are dyed for lhour at this temperature. The dyeing is then rinsed and soaped at the boil for 15 minutes. A deep yellow dyeing is obtained which has good fastness to water and light.

Other azo dyestuffs having similar properties are obtained by reacting the aminoazo dyestuffs given in the following Table 9 in. the manner described in Example 92, with (a) 2-methylarninr4-N-chloroformyl-methylamino- 6-fiuoro-s-triazine, or with equivalent parts of (b) 2-dimethylamino-4-N-ch1oroformyl-methylaminoo-fiuoro-s-triazine,

(c) 2-ethylamino-4-N-chloroformyl-n-butylamino- 6-fluoro-s-triazine, or

(d) 2-N-methyl N-phenylamino-4-N-chloroformy1- methylamino-6-fluoro-s-triazine.

TABLE 9 Shade on cel- Examplc lulose No. (a-d) Aminoazo dyestufl fibres 93 2-aminonaphthalene-5,7-disnlphonic acid 1- Yellow.

aminobenzene.

94 2-aminonaphthalene-4,8-disulphonic acid 1- Do.

amino-Z-methoxy-fi-methybenzene.

95 Z-amiuonaphthalene-G,8-disu1phonic acid 1- D0.

amino-3-methoxybenzene.

96 2-aminonaphthalene-4,8-disulphonic acid 1- Do.

N-methylaminobenzene.

97 2-aminonaphthaleneA,6,8-trisu1phonic acid 1- D0.

aminobenzene.

98 2-aminonaphthalene-4,6,8-trisu1phonic acid 1- Do.

amino-3-methylbenzene l-aminobenzene.

99 4-aminoaxobenzene-3,4,'-disulphonic acid 1- Do.

amino-@methylbenzene.

100 Z-aminonaphthalene4,8-disulfonic acid 1- Do.

aminonaphthalene-fi sulfonic acid l-methyl- 3-aminobenzene.

101 1-aminobenzene-2,5-disu1fonic acid (3-amino- Do.

phenyDurea.

EXAMPLE 102 50.3 parts of the sodium salt of the aminoazo dyestufl of the formula on H033 -so.n NH;

SOZH

(obtained by coupling diazotised 2-amino-4-acetylaminobenzene sulphonic acid with 2-hydroxynaphthalene-6,8- disulphonic acid in an alkaline medium and saponifying the acetylamino group with sodium hydroxide solution) are dissolved with a neutral reaction in 800 parts of Water. 26 parts of 2-ethylamino-4-N-chloroformyl-ethylamino-6- fluoro-s-triazine dissolved in parts of acetone are added to this solution at 0-5 the pH of the reaction solution being kept at 55.5 by the dropwise addition of sodium carbonate solution. When no more diazotisable amino groups can be traced, the dyestuif is completely precipitated by the addition of sodium chloride, isolated, stabilised with buffer salts and dried in vacuo at 40. It dissolves easily in water with an orange color.

If cotton or staple fiber is. printed by one of the usual methods with a printing paste consisting of 30 parts of this dyestulf, 200 parts of urea, 400 parts of water, 350 parts of 5%-aqueous sodium alginate solution and 20 parts of potassium carbonate, then dried, steamed for 10-15 minutes, then rinsed and finally soaped at the boil, an excellent wash-fast orange print is obtained.

By reacting equivalent amounts of the amino-azo dyestuffs listed in the following Table 10, in accordance with the procedures described in Example 102, with (a) 26 parts of 2-ethyl-amino-4-N-chlorofonnyl-ethylamino-6-fluoro-s-triazine, or with equivalent parts of lose fibers of which are given in the following Table 10, are produced.

TABLE 10 Shade on Example cellulose No. (a-g) Aminoazo dyestufi fibres 103 2-amino-4-nitrobenzene sulphonic acid Red.

1- benzoylanrinq-8-hydroxynaphtha]cue-4,6- dl-sulphomc acld, reduced.

104 2-amrno-4-nitrobenzene sulphonic acid Red.

l-acetylamino-B-hydroxynaphthalene-3,6- di-sulphonic acid, reduced.

105 2-ammo-4-nitrobenzene sulphonic acid Red.

1:benzoylamino-S-hydroxynaphthalarm-3,6- dl-sulphonic acid, reduced.

106 2-amino-4-acetylaminobenzcnc sulphonic Orange.

acid l-hydroxynaphthalene-3,6- disulphonic acid, saponified.

107 Z-amlno-st-acetylarninobenzene sulphonic Redacid l-hydroxynaphthalcne-4,6- orange. dlsulphonic acid, saponified.

108 l-anllinlobenzene-2,4-disulphonic acid Orange.

a me

2-amino-5-hydroxynaphthalene- 7-sulphonic acid.

109 Z-aminonaphthalene-l,fi-disulphouic acid Reddish alkallne orange. 2-methylamino-5- hydroxynaphthalenc-7-sulphonic acid.

110 l-aminobenzene-Z-sulphonic acid 1- Red.

(3aminobenzoylamino)-8- hydroxy'naphtha1ene-3,6-disulphonie acid.

111 2-amino-4-acetylarninobenzene sulphonic Orange.

acid 2-aminonaphthalene-5,7- disulphonic acid, saponified.

112 2-amino4-acetylaminobenzene sulphonic Yellow.

acid 1-(3-sulpl1ophenyl)-3-methyl- B-pyrazole imine, saponified.

113 1-amino-3-nitro-6-ethylbenzene 1- Reddish hydroxynaphthalene-3,6-disulfonic acid, orange. reduced.

114. l-aminobenzene-Zi-N-methylsuliamlde Red.

1-amino-8-hydroxynaphthalene-3,6- disulfonic acid.

115 l-amlnobenzone-3-N-(-,'-hydroxypropyl) -N- Red.

methylsulfonamide l-amino-S- hydroxynaphthalene-3,6-disulfonic acid.

TABLE IO-Continued TABLE 11 Shade on Shade on Example cellulose Example cellulose No. (ag) Aminoazo dyestufi fibres N o. (a-c) Metalcontaining aminoazo dyestufls fibres 11G 4-amino-3-carboxy-benzene sull'onio Orange. 125 2-amino-1-hydroxybenzene-4-sulphonic acid Violet.

acid 2-amino-5-l1ydroxy-7-suli0nic alkaline acid. l-amino-S-hydroxynaphthalene- 117 l-aminobenzene-ii-N-(fi-hydroxyethyl)-N- Red. 3,6-disulphonic acid, copper complex.

methylsultonamide l-amino- 126 2-aminc l-hydroxybcnzene-4-sulphonic acid Bordeaux. hydroxynaphthalene-4,6-disulfonic acid. alkaline 118 3-amino-4-ethoxybenzene-sulfonic acid Orange. 2-amino-8-hydroxynaphthalene- 2-amiuo5-liydroxynaphthalene-7-sulfonic 1 fi-sulphonic acid, copper complex. acid. 127. 2-amino-1-hydroxybenzene-4,6-disulphonlc Ruby.

11) l-aminobenzonc-3-N-(fl-sulfoethyl)-N- Red. alkaline nicthylsulfonamide l-amino-S- acid 2-amino-5- hydroxynaphthalone-3,6-disulfonic acid. hydroxynaphthalene-7-sulphonie acid,

120 2-aminonaphthalene-4,6,8-trisulfonic Yellow. copper complex.

acid 1-(4-aminophenyl)-3-metl1yl-5- 128 2-amino-1-hydroxybenzene-4-sulphonic acid Do. pyrazolonc. alkaline 121 l-nminobenzenc-3-N,N-bis-(y-hydroxypropyl)- Red. 2-N-methylamino-5- sulfonamidc 1-amino-8- hydroxynaphthalene-7-sulphonic acid, 11ydroxynaphthalene-3,G-disulionic acid. copper complex.

122 2,3-diamino-diphenyl-l,l-disulfimide--- Red. 129 G-nitro-1-amino-2-hydroxynapl1tlialeneA- Black.

l-benzoyl-aminoe-hydroxynaphthaleuealkaline 3,6-disulfonic acid. sulphonic acid 2-amino-5- 123 2-ai11inonapl1thalcnc-1,5,7-trlsulfonic Red. hydroxynaphthalene-7-sulphonic acid, acid 2-amino-5-hydroxynaphthalcncchromium complex 1:2. 7-sulfonic acid l-a1nino-3- alkaline D0; mcthylbcnzcnc. 130 4-nitro-2-amino-1-hydroxybenzene--- l-amino-8-hydroxynaphthalene'8,6- disulphonie acid, chromium comriiexlilfl. B1 k a a ne ac EXAMPLE 124 131. 4-nitrO-Z-amlno-I-hydroxybenzenebrown.- 0 C 1-amino-8-hydroxynaphthalene-3,6-

I u disulphonio acid, cobalt complex 1:2.

2 132 2-amino-4ocetylamino-1-hydroxybenzene-6- Reddish HO a1 allne navy 3 G H sulphonic acidl-amrno-S- blue.

| 2 hydroxynaplfthalenemdsulphonlc acid, copper comp ex, sapo e Hols NHCO N W F 133 2-amino-4-acetylamino-l-hydroxybenzene-6 Navy alkaline blue. so H N N sulphonic acid 1 -phenyla m1no-8- 3 hydroxynaphthalene-4,6-d1sulphonic acid,

' 134 e i am 1n 2 1i g hth 1 -4- Bl -n1 rooy roxynap a cue ue. NHC alkaline sulphonic acidl-amino-8- 51.7 parts of the sodium salt of the copper-contaming 3r hyiroxgnaphthalenealA-disulphonic acid,

0 re uce copper comp ex. ammomonoazo dyestuff of the formula 135 2-amino-6-acetylamino-1-hydroxybenzene-4 Ruby sulphonic acid red. 0 Cu O hydroxynaphthalenei,fi-disulphonic acid,

| copper complex, saponified.

136-. Z-amino-G-acetylamino-l-hydroxybenzene-4- Yellow H0 s N: sulphonic acid 1-(2,5- brown.

disulphophenyl)-3-methyl-5-pyrazolone,

copper complex, saponified. H0 S NH, 137 l-hydroxy-Z-amino-fi-methylsulfonylbenzcno Ruby 2-amino-8-hydroxynaphthalenered. 3,6-disullonic acid, copper complex. 0 11 138 3-amlno-4hydroxy-benzene sulfonic acid Yellow.

T liay-amnptphenyll aceitgl acetic aci am e,coa com ex (obtarned by coupling, d1a zot1zed 2-am1no-l-hydroxyben- 5 139 gg violet 1ene-7-sulfonic acid in an alkaline medium and treat ng 140 1 2 i 6b .5.N (5 Ruby the aminomonoazo dyestutf obtained wlth an agent giving memo?!YeihyD-N-amylsulfonamlde 2-amino-8-hydroxynaphthalene-3,6-

off copper) are dissolved in 1000 parts of water. At disulgomc acid, copper complex,

0-5, a solution of 27.2 parts of 2-ethylamino-4-N- chloroformyl-ethylamino-6-fiuoro-s-triazine in 100 parts of acetone is added and the pH of the reaction solution is kept at 5-5.6 by the addition of sodium carbonate solution. When no more free amino groups can be traced,

the new dyestuff is completely precipitated by the addition EXAMPLE 141 of sodium chloride, buffer salts are added and the dyestutf is isolated and dried in vacuo at 40. The dark powder dissolves in water with a ruby red color.

If cotton is padded with a 2% -solution of this dyestulf which also contains 2% of sodium bicarbonate, the im- 8 pregnated goods are stored for 4 hours at room temperature, then soaped at the boil, and rinsed, a ruby red Hoes SOKH dyeing is obtained which has very good wet and light fastncss properties. 0 H

z 5 Other metal-containing aminoazo dyestuffs are given 5 i N in the following Table 11, which are reacted as described NH- NHCONW W in Example 124 with I N N $0 11 (a) 2-ethylam1no-4-N-chloroformyl-ethylam1n0-6- fiuoro-s-triazine, NHC H,

or with equivalent amounts of (b) Z-N-methyl-N-ethylamino-4-N-chloroformylethylamino-6-fluoro-s-triazine, or

(c) Z-dimethylamino-4-N-chloroformyl-methyl- 48.9 parts of 1 amino-4-(4'-aminophenylamino)- amino-6-fluoro-s-triazine. anthraquinone-Z,7-disulphonic acid are added at 20-25 in 500 parts of 30% oleum. The reaction mixture is stirred for 24-36 hours at 20-25. The reaction mixture is then poured onto ice and the dyestuff which precipitates of the formula NHz is filtered off.

The filter cake, in the form of the sodium salt, is dissolved in 1000 parts of water. A solution of 26 parts of 2 ethylarnino 4-N-chloroformyl-ethylamino-6-fluoro-striazine in 100 parts of acetone is added dropwise to this solutionjat 0l0 and the pH is kept at 5-5.5 by the simul- 20 taneous addition of sodium carbonate solution. On completion of the condensation, the new dyestufi is precipitated. by the addition of sodium chloride, isolated, stabilized with buffer salts and dried in vacuo at 40. It dissolves in water with a blue color.

If regenerated cellulose is padded with a 2%-solution of this dyestulf which also contains g. of sodium bicarbonate and g. of urea per liter, the impregnated goods are dried and heated for 2 minutes at -110", then a pure blue dyeing is obtained which has very good fastness to washing and light.

Other aminoanthraquinone dyestuffs are given in the following Table 12 which are condensed as described in Example 141 with (a) 2-ethylarnino-4-N-chloroformyl-ethylamino-6- fluoro-s-triazine,

or with equivalent parts of (b) 2-diethylamino-4-N-ch10roformyl-methylamino-6- fluoro-s-triazine,

(c) Z-methylamino-4-N-chloroformyl-methylamino- 6-fiuoro-s-triazine,

(d) Z-N-methyl-N-(4'-chlorophenylamino)-4-N- chloroformyl-methylamino-6-fluoro-s-triazine,

(e) Z-N-methyl-N-(4-ethoxyphenylamino)-4-N- chloroformyl-methylamino-6-fluoro-s-triazine,

(f) 2-phenylthio-4-N-chloroformyl-ethylamino- 6-fluoro-s-triazines,

whereby reactive dyes of similar properties as those described in the preceding examples are obtained. Cellulose fibers dyed therewith have the shades given in the last column of Table 12. 1

TABLE 12 Shade on Example cellulose N0. (a-f) .Aminoanthraquinone dyestuffs fibres 142 T) IIIHQ Blue.

A s 03H V N H:

( NH s 03H I S 03H 143-- fi) 1TH: D0.

HMS-@ s our Y I O NH- S 0311 144..:......: (ll) IIIHz D0.

H O: S V

H l O NH- NH2 l S OaH 145.452.": ITTH: DO.

A s 03H TABLE 12-Continued Shade on Example cellulose No. (a-t) Amlnoanthraquinono dyestuffs fibres 146 NH: Blue.

A-S 03H HOaS Y Nn--sonr 147.-...:. r: fl) I[ IHz Do.

4@ s our H038 0 NH- NH:

tom

dried in vacuo at 40". It corresponds to the formula 0 given at the beginning of this example. EXAMPLE 14 If cotton is padded at with a 2% solution of this dyestuff which also contains 20 parts of sodium bicarbon- I O NH O H ate and 200 parts of urea per litre, and the impregnated Cu T 2 z 5 goods are dried, then heated for 4 minutes at 130140 aL- J( a )2 I\IIHC L F and finally soaped at the boil for 30 minutes, then a pure 5 W turquoise blue dyeing is obtained which has very good N wet and light fastness properties. Other amino-phthalocyanine dyestuffs are given in the IlIHCZHB following Table 13, which are condensed as described in In this formula:

EPc represents the phthalocyanine structure.

57.6 parts of copper phthalocyanine are heated for 3 hours at 145 in 270 parts of chlorosulphonic acid. The solution is then cooled to and 33.5 parts of thionyl chloride are added dropwise within 1 hour. The mixture is stirred for 3 hours at 70-75 then cooled to room temperature and poured onto 1500 parts of ice. The suspension formed is filtered off and the precipitate is washed with 500 parts of 1% hydrochloric acid. The filter cake is then slurried in 500 parts of water and 300 parts of ice, stirred with 15 parts of m-aminoacetanilide and the pH is adjusted to 7 by the addition of aqueous ammonia solution. The temperature is then slowly allowed to rise to 40-50", the pH of the suspension always being kept at 7.0-7.5 by the addition dropwise of ammonia solution. As soon as no more primary amine can be traced, 270 parts of 30% hydrochloric acid are added. The mixture is heated for 3 hours at -90 and in this way the acetylamino group is saponified.

The amino-phthalocyanine dyestutf of the formula CuPc l T (s03N3)2 11TH] wherein Pc has the meaning given above, is so obtained.

This dyestuff is then isolated by filtration, again slurried in 1000 parts of water which is 0-5 cold and the pH of the suspension is adjusted to 8.0 with dilute sodium hydroxide solution. A solution of 26 parts of 2- ethylamino-4-N-chloroformyl ethylamino 6 fiuoro-striazine in parts of acetone is poured into this suspension. Condensation is performed at 0-5 while stirring well and the hydrochloric acid liberated is neutralised by the addition dropwise of dilute sodium carbonate solution. On completion of the reaction, the new dyestuff is completely precipitated by the addition of sodium chloride, isolated in the presence of a buffering agent and Example 148 with (a) 2-ethylamino 4 N chloroformyl-ethylamino-6- fiuoro-s-triazine,

or with equivalent parts of (b) 2-diethylamino-4 N chloroformyl methylamino- 6-fiuoro-s-triazine,

(c) 2 methylamino4-N-chloroformyl methylamino-6- fluoro-s-triazine,

(d) 2-(4'-methylphenylthio) 4 N chloroformylmethylamino-6-fluoro-s-triazine,

(e) 2-morpholino 4 N chloroformyl methylamino- 6-fluoro-s-triazine, or

(f) Z-piperidino 4 N chloroformyl propylamino-6- fiuoro-s-triazine.

The resulting reactive dyes have similar good properties as those of the preceding examples, and dyeings produced therewith on cellulosic fibers, exg. cotton, have the shades given in the last column of Table 13.

EXAMPLE 152 S 03H OH I [3113 N N=N NHCO- IE j-F N H033 Ny OaH NHCHs 23.9 parts of 2-amino-8-hydroxynaphthalene 6 sul- 10 phonic acid are dissolved in 400 parts of water, the pH being adjusted to 6:5 with sodium carbonate, and the solution is cooled to 0-5". A solution of 24 parts of 2- methylamino-4-N-chloroformyl-methylamino 6 fluoroas described in Example 152 and the condensation products are coupled as described in the same example, with the dia'zo components given in column II. The shades of dyeings with the resulting reaction dyes on cellulose fibers are given in column IV of Table 14.

TABLE 14 I II III IV Shade on Example cellulose No. (a-d) Diazo component Acylatable coupling component; fibr 153 l-aminobenzene-2-sulphonic acid l-amino-8-hydroxynaphthalene-3,6-disulphonic acid Red. 154 2-aminonaphthalene-l-sulphonlc acid..- do Blueish red. l-aminobenzene-Z-sulphonic acid l-amino-B-hydroxynaphthalene-4,6-disulphonic acid Red. 2-aminonaphthalene-1,5-disulphonic acid do Blueish red. 157 l-aminobenzene-2,4disulphonic acid. 1-(4'-aminophenyl)3-methyl-5-pyrazolone Yellow. 158 1-aminobenzene-2,fi-dlsulphonlc acid 2amino-5-hydroxynaphtha1ene-7-su1phonie acid Orange, 159 l-aminobenzene-Z-sulphomc acid 2-methylamino-5-hydroxynaphthalene-7-sulphonic acid Do. 160 4-aminoazobenzene-3,4-di5u1phonic v do s r t.

s-triazine in 100 parts of acetate is added dropwise Within 15 minutes at this temperature and the pH of the reac- EXAMPLE 161 (13113 so H N CH C=N a l a)? N(CH3)2 5 3E N N=N =0 1 l l N H--C O-N -01 0H N tion mixture is kept at 4.5-5.5 by the addition of sodium carbonate solution. As soon as no more unchanged amino compound can be traced, 30 parts of sodium bicarbonate are added to the solution and then a solution of 30.3 parts of diazotised 2-aminonaphthalene 1,5 disulphonic acid is poured in. On completion of the coupling, sodium chloride and buffer salts are added to the reaction mixture, the precipitated dyestufi is filtered ofl, washed with sodium chloride solution and stabilised with buffer salts. After drying in vacuo at a red powder is obtained which dissolves in water with a red colour. If mercerised cotton is padded with a 2% solution of this dyestufi at 20, dried and then treated with a 1% sodium hydroxide solution which also contains 30% sodium chloride, then steamed for 30 seconds at 100-103, finally rinsed and soaped at the boil for 30 minutes, then a red dyeing is obtained which has very good wet and light fastness properties.

The following Table 14 lists the main moieties of other dyestuffs according to the invention having similar properties which are obtained by condensing the coupling components containing amino groups given in column III with 18.8 parts of 1,3-diaminobenzene'4-sulphonic acid are dissolved in 400 parts of water at a pH'-'value of 44.5 and the solution is cooled to 0-5 Then within 15 minutes 27 parts of 2-dimethylamino-4-N-chloroformyl methylamino-fi-chloro-s-triazine dissolved in parts of acetone together with an aqueous solution of sodium carbonate are dropped into this solution in such a manner that the pH-value of the reaction mixture is maintained at 44.5. As soon as the reaction is completed, the reaction product is precipitated by addition of sodium chloride, filtered off, dissolved in 400 parts of water and diazotised at 05 with 25 parts of 30% hydrochloric acid and 6.9 parts of sodium nitrite. The resulting diazonium compound is coupled at a pH-value of 4-5 with a solution of 48 parts of the condensation product of 1-(2'-sulphonic acid-5'-aminophenyl) 3 methyl 5 pyrazolone and Z-dimethylamino 4 N chloroformyl methylarnino- 6-chloro-s-triazine (produced from the two components under the conditions described in Example 152). After completion of the coupling, the new dyestulf is precipitated with sodium chloride, filtered oif and washed with diluted sodium chloride solution. After drying in vacuo at 50, 3. yellow powder is obtained which dissolves in water with a yellow colour.

If cotton or staple fiber is dyed with the new dyestuif according to the application methods described in the preceding examples, a deep yellow dyeing of good fastness properties to light and wet is obtained.

Further dyestuffs with similar properties are obtained if the diazo and coupling components listed in the following Table 15 are reacted according to the conditions given in Example 161 with (a) Z-dimethyla'mino-4-N-chloroformyl methylamino 6 chloro-s-triazine or equivalent parts of (b) 2-methylthio-4-N-chloroformyl methylamino 6 chloro s triazine or (c) Z-dimethylamino- 4 N chloroformyl methylamino 6 fiuoro-s-triazine and are then diazotized and coupled as described in the above example to form dyestuffs, the shade of which on cellulose fibers is given in the last column of the Table 15.

59.6 parts of the copper complex compound of the aminoformazane dyestufi of the formula (obtained by coupling diazotized 6-acetylamino-2-aminol-hydroxybenzene-4-sulphonic acid with the hydrazone from benzaldehyde and phenylhydrazine-Z-carboxylic- TABLE Shade on Example cellulose No. (a-c) Diazo component; Coupling component fibres 162 1,3-diaminobenzeneA-sulphonie acid. 1-am ino-8-hydroxy-naphthalone-4,6-disulph0nic acid Red. do 2-am1no-8-hydroxy-naphthalene-6-sulphonio acid Red. d 2'ethylarnino-8-hydroxy-naphthalene-G-sulphonie acid. Red.

do l-(tammophenyi)-5-pyrazolone-S-carboxylie acid"... Yellow 166 1,4-diaminobcnzene-3-sulphonio acid d0 Do.

EXAMPLE 167 acid-4-sulphonic acid reaction with a copper salt and saponification of the acetylamino group) are dissolved at a pH-value of 6-6.5 in 600 parts of water. 33 parts of 2-phenoxy-4-N-chloroformyl-methylamino 6 chloro-striazine dissolved in 80 parts of benzene together with an aqueous solution of sodium carbonate are dropped into this solution within one hour at 20-25 so that the reaction r p CH3 mlxture remains neutral. As soon as no more starting material can be traced, the dyestuff is precipitated by C00 0 l addition of sodium chloride, filtered off, washed with Q diluted sodium chloride solution and dried cautiously in o i 40 vacuo. It is a dark powder which, dissolved in warm S0311 water, gives a blue colour. N The 2 phenoxy 4 N-chloroformyl-methylamino-6- ii I chloro-s-triazine mentioned in the preceding example is y obtained by known methods by reacting 1 mol of cyanuric C chloride in a first ste with 1 mol methylamine and in a P second step with 1 mol phenol and finally treating the condensation product with phosgene in toluene.

By using equivalent amounts of the metal-containing aminoformazane compounds shown in columns II and III of the following Table 16 and the acylating agents listed in column IV, and by maintaining the reaction conditions described in the preceding Example 167, further dyestuffs according to the invention are obtained which have similar properties.

TABLE 16 I II III 1V V Shade 1on cellu- Exam le 050 No. p Aminoformazane dyestufl Metal Aeylating agent fibres 168 N -(2-hydroxy-3-aminophenyl-5-sulphonic lacid)1-fN-(2- Cu 2-di1fi1ethy1tarnino-4-Nchloroformyl-methylamino-fi- Blue.

l1 l-4 ul h acid sion 0 azanc. c oro-s-nazlne. 169 fi dgfii l fii"f 1fi fnnl gfiujui f Cu 2-dimetliylaminot-N-chlorol'ormyi-ethylamino-B-fiuoro-s- Do.

triazine. 170 N-(2-hydroxy-3-aminophenyl-B-sulphonic acid)-N-(2'- Cu .do D0.

1ydroxy-phenyl-3,5 -disulphonic acid)-ms-phcnyl- 171 .g d b i f ji Cu 2ethylthio-4-N-ehloroformylethylaminofi-ehloro-S- D0.

triazine. 172 N-(2-hydroxy-3-aminophenyl-5-sulphonic acid)-N-(2- Cu 2-dimethylarnino-4-N-chlorolormyl-methylaruino-6- D0.

carboxyPheny1-4sulphonic acid) -ms-o-sulphom'e acid chloro-s-tnazine.

h 1- a 173 d m f ff f Cu 2-dimethylaminoi-N-chloroformyl-mcthylammo-B- D0- fluoro-s-triazine. 174 N-(2-hydroxy-3-aminophenyl-fi-sulphonic aeid)-N-(2- Cu do D0.

hydroxyphcnyl-B,5-disulphonio aoid)-ms-o-sulphonic acid phenyl-formazane. d0 Cu 2-dimethylammo-4-N-chloroformyl-methylammob' D0.

chloro-s-triazine. 6 .do Cu 2phenylthio-4-N-chloroiormyl-methylammo-G-chloro-s- Du.

triazine.

phenoxy, lower alkoxy-substituted phenoxy, lower alkythio, phenylthio, halogen-substituted phenylthio, lower alkyl-substituted phenylthio, lower alkoxysubstituted phenylthio, lower alkylamino, di(l0wer)- alkylamino, phenylamino, N-lower alkyl-N-phenylamino, N-lower a1kyl-N-halogenphenylamino, N-lower alkyl-N- lower alkylphenylamino, N-lower alkyl-N-lower alkoxyphenylamino, piperidino or morpholino, halogen being chloro or bromo.

2. An anthraquinone dyestulf according to claim 1 wherein X is a dialkylamino radical, each alkyl moiety of said radical having up to four carbon atoms.

3. An anthraquinone dyestuif according to claim 1 of the formula ii (soft I g/ a 3 NH:

I NH R N 3 ii NH soa I N (QM! bimbo-NI ENE-02H N .N \w-aai n (Q 0 (lower: alkyl) N C N l X wherein wherein selected from the group of lower alkoxy, phenoxy, halogen-substituted phenoxy, lower alkyl-substituted Q+ represents hydrogen ion, ammonium ion or sodium or potassium metal ion.

References Cited UNITED STATES PATENTS 3,110,710 11/1963 Rattee et al 260249 XR JOHN M. FORD, Primary Examiner US. Cl. X.R.

260-2472 A, 249.5, 146 T, 153, 242; 8-39, 42 B, 163 

